Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, Shaanxi, China. and Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
Published: April 2021
AI Article Synopsis
Article Abstract
Oxygen evolution and reduction reactions are fundamental processes in biological energy conversion schemes, which represent an attractive method for artificial energy conversion for a world still largely depending on fossil fuels. A range of metalloenzymes achieve these challenging tasks in biology by activating water and dioxygen using cheap and abundant transition metals, such as iron, copper, and manganese. High-valent metal-oxo/oxyl, metal-superoxo, and/or metal-(hydro)peroxo species are common reactive intermediates that are found in the O-O bond formation and activation reactions. The transient nature of the metal-oxygen intermediates has, however, prevented their isolation and characterization in most cases. As a consequence, unambiguous mechanistic assignments in the O-O bond formation and cleavage processes in biological and chemical entries remain elusive, especially for the intermediates and mechanisms involved in the O-O bond formation reactions. This viewpoint article aims at summarizing the information obtained to date in enzymatic and biomimetic systems that fuels the debate regarding the nature of the active oxidants and the mechanistic uncertainties associated with the transition metal-mediated O-O bond formation and cleavage reactions.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Jiangwan Campus, Fudan University, Shanghai 200438, China.
The phosphaguanidinate rare-earth-metal bis(aminobenzyl) complexes [(PhP)C(NCHPr-2,6)]Ln(CHCH NMe-) (Ln = Y(1-Y) and Lu(1-Lu)) were synthesized by the protonolysis of (PhP)[C(NHR)(NR)] (R = 2,6-(Pr)CH) with Ln(CHCHNMe-) (Ln = Y and Lu). Interestingly, the ring-opening rearrangement product [-MeNCHCHC(NCHPr-2,6)]Lu(CHCHNMe-)[O(CH)PPh] (2) was obtained when the acid-base reaction was carried out in THF solution at 60 °C for 36 h. Additionally, the trinuclear homometallic yttrium multimethyl/methylidene complex {[(PhP)C(NCHPr-2,6)]Y(μ-Me)}(μ-Me)(μ-CH) (3) was synthesized by the treatment of 1-Y with AlMe (2 equiv.
State Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China.
Metal-organic frameworks (MOFs) are promising electrochemiluminescent (ECL) nanoemitters. Great endeavors have been made to optimize the inherent luminescent properties, yet most MOFs suffer from poor coreactant activation ability, resulting in limited ECL. Therefore, it is urgent to integrate and design efficient catalytic centers within MOFs.
The crystal structure of the title compound, [Ni(CHN)(NO)]NO, at room temperature, has monoclinic (2/) symmetry. The structure displays inter-molecular hydrogen bonding. The nickel displays a distorted bipyramidal geometry with the symmetric bidentate bonded nitrate occupying an equatorial site.
Tianjin Key Lab of Indoor Air Environmental Quality Control, School of Environmental Science and Technology, Tianjin University, Tianjin 300350, China; State Key Laboratory of Engines, Tianjin University, Tianjin 300350, China. Electronic address:
The accumulation of intermediate products on the catalyst surface caused by insufficient oxygen activity is an important reason for the poor activity of catalysts towards oxygenated volatile organic compounds (OVOCs). CoMnO@MnO heterogeneous catalysts were fabricated to decipher the interfacial oxygen activation mechanism for efficient acetone oxidation. Experimental and theoretical explorations revealed that oxygen vacancies were easily formed at the interface.
The one-step oxidation of benzene to phenol represents a significant and promising advancement in modern industries focused on the production of high-value-added chemical products. Nevertheless, challenges persist in achieving sufficient catalytic selectivity and preventing over-oxidation. Inspired by copper enzymes, we present a nonsymmetric dicopper complex ([CuII2(TPMAN)(μ-OH)(HO)], 1) for the selective oxidation of benzene to phenol.
